Selected bis(dialkylamino)alkoxymethanes and tetrakis(dialkylamino)ethylenes and thesynthesis thereof



United States Patent 3,239,519 SELECTED BIStDIALKYLAM'I-NOMLKQXYMETH- ANES AND TETRAKIS(DIALKYLAMINO)ETH- AND THE SYNTHESIS THEREOF Hilmer E. Winherg, Wilmington, Del., assignor to E. I. (in Pont, de N emours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Filed Feb. 20, 1962, Ser. No. 174,404 35 Claims. (Cl. '260'246) This application is a continuation-in-part of my copending application Ser. No. 91,589, filed Feb. 27, 1961, and now abandoned, which in turn is a continuation-inpart of my copending application Ser. No. 836,062, filed August 26, 1959, and now abandoned in favor of the continuation-impart application thereof, S.N. 91,590, filed Feb. 27, 1961.

This invention relates to, and has as its principal objects provision of, a new class of b-is(disu-bstitutedamino)al koxymethanes and their preparation, a new process generic to the preparation of tetrakis(disubstitutedamino)- cthylenes (late-rnatively, per(tertiaryamino)ethylenes), and certain new tetrakis(di substitutedamino)ethylenes.

Pruett et al., J. Am. Chem. Soc. 72, 3636 (1950)., prepared the first member of the series of the tetrakis- (disubstitutedamino)ethylenes, i.e., tetr-akis(dimethyl- -am in:o)ethylene (TMAE), by the reaction of dirnethylamine with chlorotrifiuoroethylene. As is true of most first members of series of organic compounds, TMAE is diiferent from the, higher straight chain analogs and is especially different from the somewhat related compounds wherein two hydrocarbon substituents on amino nitrogen (the same or different) are together joined to form nitrogen heterocyclic structures of from five to seven ring members. The difference between the first member of the series and the higher analogs and somewhat related cyclic compounds exists not only in the properties of the compounds but extends to operable methods of preparation therefor. For instance, while the reaction between chlorotrifluoroethylene and dimethylamine proceeds smoothly to afiord TMAE, a similar reaction does not take place with even the next member of the secondary amine series, i.e., diethylamine.

Furthermore, this method of preparation not only does not proceed with the next higher homolog diethylamine, but does not proceed with any of the still higher homol-ogs nor with the somewhat related cyclic secondary amines. Surprisingly, the reaction of chlorotrifluoroethylene with any secondary amine thus far tried other than dimethylamine, including both arcyclic and cyclic, has resulted in the formation of no identifiable amount of the tetrakis (disubstitutedamines) expected from analogy with the Pruett et al. reaction.

While it is not known with certainty, a reasonable explanation for the inoperability of the halogenated ethylene/secondary amine reaction in forming the higher tetrakis(disubstituted amino)ethylenes can be found in steric factors. Thus, the reaction to form TMAE appears to proceed through a conjoint addition/elimination mechanism. With the relatively small molecular size of dimethylamine, there is sufiicient space around the carbon-carbon linkage of the haloethylene to permit addition of the requisite amino hydrogen and the remaining other moiety of the entering secondary amine across the C C linkage of the haloethylene, followed by elimination of HX, so that this reaction can proceed four times to give the TMAE product. However, with the larger groups on the amine nitrogen in the higher straight chain homologs, and in particular with the more demanding space factors necessarily encountered with the cyclic amines where there is no longer free rotation 3,239,519 Patented Mar. 8, 19,66

about the amine-.to-ca-rbon linkages, there is simply not enough space around the carbon-carbon linkage to permit this reaction to occur the requisite four times to form the tetrakis (disubstitutedamino)ethylene. To illustrate specifically with diethyl-amine and chlorotrifluoroethylene, the only product obtained by pushing the reaction as far as it appears to go is 1,1-bis(diethylamino)- 2-chloro-2-fiuoroethylenc, i.e., the addition/elimination reaction can only be a'chieved twice.

It has now been found, surprisingly, in contrast to the foregoing findings that the tetrakis(disubstitutedamino)- ethylenes and the bis(disubstitutedamino)hydrocarbyloxymethanes intermediate thereto, the latter generically anew class of compounds, can be prepared by the ready reaction between the requisite basic secondary amine and any amide acetal, i.e., any disubstitutedamino-dihydrocarbyloxymethane, in accord with the following stoichiometry:

wherein the Rs, which can be alike or difierent, are monovalent alkyl or cycloalkyl radicals, generally of no more than eight carbons each, which can be together joined (in a divalent radical) to form with the intervening nitrogen a heterocycle of from three to seven ring members; the Rs which can also be alike or different, or together joined, are monov'alent (or divalent) alkyl, aryl, aralkyl, alkaryl, or cycloalkyl radicals, generally of no more than eight carbons each, and when together joined, form with the two oxygens and intervening carbon a 1,3-dioxa'heterocycle of from five to seven ring members; and the R"s which can also 'be alike or different or together joined, are monovalent (or divalent) alkyl or cycloalkyl hydrocarbon or oxaand/or azahydrocarbon radicals of no more than eight carbons each, each nitrogen carrying no more than one methyl group and, in the case of the divalent radicals, no more than from two to six carbons per divalent radical. In any event, when the two R"s are together joined, they form with the indicated amino nitrogen a monoazacarbocycle, an oxaazacarbocycle, or a diazacarbocycle of from three to seven ring members.

For reasons of easier conversion to the desired new bis disubstitutedamino hydrocarbyloxymethanes and tetrakis (disubstitutedamino)ethylenes, it is preferred to use the short chain hydrocarbon amide acetals, i.e., the 1,1- di (hydrocarbyloxy) disub stitutedaminomethanes wherein the substituents on the nitrogen (R in the above) are of short chain length, ideally straight chain saturated hydrocarbon and oxaand azahydrocarbon radicals of no more than six chain members. Also strongly preferred for ease of preparation are the cyclic products, i.e., those where two R" radicals on the same nitrogen or on different nitrogens on the same carbon are joined together to form, respectively, monoazaand diazacarbocycles.

The over-all equation can be represented as:

However, such a summation equation does not fully reflect the equilibrium character nor the true product distribution, and it is believed the three foregoing simpler equations illustrate the reaction stoichiometry better.

In its product aspects the present invention is generic, not only to the bis(disubstitutedamino)hydrocarbyloxymethanes, but also such products wherein the methane hydrogen has been replaced by a monovalent hydrocarbyl radical, i.e., the a,u-bis(disubstitutedamino)-a-hydrocarbyloxyhydrocarbons. Thus, the invention is generic both processand product-wise in accord with the following stoichiometry:

where the Rs, R"s, and Rs have the same significance as previously described and R is a monovalent hydrocarbon radical of up to 8 carbons and free of aliphatic unsaturation.

The only significant diiference between the chemistries of these two segments of this invention, i.e., between the amide acetals, which are by definition formamide derivatives, and the amide ketals, which by definition are free of hydrogen on the carbon to which the nitrogen and the two hydrocarbyloxy radicals are linked, is that the amide ketals do not undergo the last stage of the reaction indicated for the amide acetals, i.e., elimination of two more molar proportions of the hydroxyhydrocarbyl compound, i.e., alcohol or phenyl, and dimerization to form the tetrakis (disubstitutedamino ethylenes.

It may be noted, however, that, when at least one of the Rs is an azahydrocarbon (as in a diamine; see Examples X, XI, XII, and XIII, below), both the amino groups present react readily. The product is a cyclic compound in which the nitrogens attached to a single carbon are also joined through another radical in a ring structure. The novel products of the invention are thus of four different types, i.e., diamino alkoxyrnethanes and tetrakis-diamino ethylenes in each of which the two nitrogens on one carbon may be in (Q below), or not in, a cyclic structure with the aforementioned carbon. The formulas for these four types of compounds may be written, essentially elaborating upon the symbol R" used in the process equations above, as follows:

In these formulas R is alkyl, aryl, aralkyl, alkaryl or cycloalkyl of up to 8 carbons; R and R are, individually, monovalent alkyl, cycloalkyl, oxahydrocarbon, azahydrocarbon, or oxaazahydrocarbon of up to 8 carbons, each depicted nitrogen carrying no more than one methyl, or, jointly, divalent alkylene, oxahydrocarbon or azahydrocarbon of 2-6 carbons; R and R are, individually monovalent alkyl, cycloalkyl, oxahydrocarbon, azahydrocarbon, or oxaazahydrocarbon of up to 8 carbons, each depicted nitrogen carrying no more than one methyl, or, jointly, divalent alkylene, oxahydrocarbon or azahydrocarbon of 2-6 carbons; and Q is alkylene of 1-4 carbons.

Formulas I and II above represent diamino alkoxymethanes while III and IV represent tetrakis-diamino ethylenes. II and IV also represent the cyclic structures obtained from diamines, i.e., compounds of formula R NH where at least one R" is azahydrocarbon.

As can be seen from the equations for the process, the reaction is basically a substitution or substitution/condensation reaction in which the entering secondary amine moiety is substituted for the disubstitutedamino moiety of the amide acetal or ketal coreactant and, if sufficient entering secondary amine is present and the reaction conditions are sufiiciently rigorous, the entering secondary amine also displaces one of the hydrocarbyloxy moieties of the amide acetal or ketal to put another secondary amino substituent in place thereof and form, as a condensation product, the corresponding hydroxhydrocarbyl compound, i.e., the corresponding alcohol or phenol, and the bis(disubstitutedamino)monohydrocarboxyl product.

Generally speaking, the entering disubstituted amine will be of longer chain length, i.e., higher carbon content, than the disubstitutedamino moiety of the amide acetal coreactant. The reaction will be effected simply by mix ing the two coreactants, generally with the secondary amine coreactant in excess, and heating. The resulting substituted secondary amine corresponding to the secondary amino moiety of the amide acetal coreactant will be removed by distillation as the reaction proceeds, as will any resulting alcohol or phenol through the condensatio substitution of a second disubstitutedamino fragment for one of the hydrocarbyloxy fragments of the amide acetal or ketal. As the reaction conditions become more rigorous, e.g., in the average temperature range 25 C. to 125 C., more of the bis(disubstitutedamino)hydrocarbyloxy product will result. In a similar fashion with the formamide acetals as the reaction conditions are made still more rigorous, particularly in the temperature range 125 C. to 250 C., more of the fully substituted/condensed product, i.e., the tetrakis(disubstitutedamino)ethylene, will be formed. Formation of these latter products, i.e., the tetrakis(disubstitutedamino)ethylenes, will be found not only in the higher temperature ranges but also in the lower ranges when the less sterically hindered disubstituted amine coreactants are involved. This is especially true for the short chain diamines resulting in the cyclic amino ethylenes where steric factors, e.g., preferential ring formation, are significant since some of these products are obtained in the C. range. Generally speaking, if less than six carbon atoms are found in the su-bstituents on nitrogen in the entering disubstituted amine coreactant, steric hindrance will not disfavor the formation of the tetrakis(disubstitutedamino)ethylene.

The reaction is an easy one to carry out, requiring only that the necessary two coreactants be brought together and heated. To avoid possible side reactions and other complicating factors, the reaction is normally carried out in a dry, inert atmosphere, e.g., dry N The substituted secondary amine corresponding to the disubstitutedamino moiety of the starting amide acetal coreactant will normally be removed by simple distillation. Ideally speaking, this disubstituted amine will be sufficiently low boiling that it can be permitted to vent as a gas through the reflux condenser of the distillation head normally used. The alcohol or phenol resulting from the condensation reaction between a second molar proportion of the entering secondary amine and one of the hydrocarbyloxy moieties of the amide acetal coreactant will normally be condensed and removed as a liquid distillate as formed.

While no reaction solvent at all is required, for ease and convenience it may sometimes be desirable to use an inert hydrocarbon or hydrocarbon ether solvent in excess to assure good contact between the two coreactants. Since many of the lower alcohols form azeotropes with various of the hydrocarbon solvents, it frequently develops that the alcohol/hydrocarbon solvent azeotrope simply is distilled from the reaction mixture, and when azeotrope formation ceases, the reaction for the formation of the bis(disubstitutedamino)hydrocarbyloxymcthane is substantially complete. Under such conditions, i.e., using an inert solvent, the reaction mixture normally will not reach the temperatures necessary for the formation of the tetrakis(disubstitutedamino)ethylenes except, as mentioned before, for the diamines and resultant cyclic aminoethylenes. If the tetrasubstituted products are the desired ones, either no reaction diluent is used and the reaction is driven to completion solely thermally or, for

convenience, an inert reaction solvent is used and the reaction driven to completion therewith to the formation of the bis(disubstitutedamino)hydrocarbyloxymethane. The reaction diluent will then be removed by distillation and the tetrakis(disubstitutedamino)ethylene formed by further heating of the bis(disubstitutedamino)hydrocarbyloxymethane.

From the foregoing, it is apparent that the reaction between the indicated secondary amine and the amide acetals and ketals involves a multistage equilibrium between the two said coreactants and three products:

(1) The mono(di-longer chain substituted)aminodihydrocarbyloxy product, i.e., the product resulting from substitution of the disubstitutedamino moiety of the amine coreactant for the disubstitutedamino moiety of the amide acetal or ketal coreactant;

(2) The his(di-longer chain substitutedamino)hydrocarbyloxy product, i.e., the product resulting from substitution of the di-longer chain substituted amino moiety of the amine :coreactant for one of the hydrocarbyloxy groups of the product 1; and, for the formamide acetals,

(3) The tetrakis(di-longer chain substitutedamino) ethylene resulting from complete removal of hydrocarby1oxy fragments from the product 2, followed by coupling of the residue to form the substituted ethylene.

As is true of all such multistage equilibrium reactions, the identity of the major product will vary as a function of the controlling variables-here, the reaction temperature, the molar proportions of the coreactants, and the basicity and steric configuration of the amine. Operating in the lower ranges needed to effect any reaction at all, e.g., in the range C. to 80 C., will result in a significant portion of the product being 1. Operating with an excess of the secondary amine coreactant and in the higher temperature ranges, e.g., in the range 80 C. to 125 C., a major portion of the product will be the bis(disubstitutedamino)monohydrocarbyloxymethane of 2. Operating with a major excess of the secondary amine and in the higher temperature ranges, e.g., in the range 125 C. to 250 C., but only for the formamide derivatives with those secondary strongly basic amines which contain a total of less than six can-hon substitutents and a total of less than six carbon and hete-roatom substituents on each amino nitrogen, a majority of the product will be the fully substituted tetr-akis(disubstitutedamino) ethylenes.

It will be understood that the products numbered 1., above, i.e., the mono (di-longer chain substituted)aminodihydrocarbyloxy product, can be isolated if desired and/or converted to the bis-compound numbered 2 by further reaction with the secondary amine coreactant. The bis-compound can, in turn, also be separately isolated and/ or converted to the tetrakis-product, 3, thermally.

As is true of all such substitution/elimination reactions, the kinetics and degree of completion, as 'well as ease of formation, will vary with the chain lengths of the substitutents on the coreacting amide acetals and ketals and secondary amines. Generally speaking, the reaction which will be effected first and g0 furthest to completion at any given reaction temperature will be the one that involves elimination of the lowest boiling product. Thus, the longer the carbon chain is on the amide moiety of the starting amide acetal or ketal coreactant, the more difficult it is for exchange and elimination to be eifected by the entering secondary amine moiety of the amine coreactant. The same holds true for the chain length of the hydrocarbyloxy moiety of the amide acetal or ketal versus the entering amine moiety of the amine coreactant. Accordingly, for use of preparation, it will be apparent that the preferred amide acetal and ketal coreactants will have the shorter chain substituents in both the amine moiety and acetal or ketal moieties thereof. Thus, for an over-all reaction efficiency basis, the most outstanding and useful such coreactant is the dimethyl acetal of N,N-dirnethylformamide, i.e., apt-dimethoxytrimethylamine.

Generally speaking, it is believed that the foregoing Reactions 1 and 2 occur concomitantly, and, practically speaking, it is not believed that Reactions 1 and 2 can be effected separately quantitatively. It is to be understood that Reaction 3, i.e., the formation of the tetrakis(disubstitutedamino)ethylenes, can function only with formamide acetals. The degree of efficiency of this last reaction also depends on the basicity of the secondary amine coreactant, with increasing base strength increasing the conversion to the ethylene at any given temperature. Steric factors also are important with respect to Reaction 3, and it is only in the instance where no steric crowding exists that the tetrasubstituted ethylenes can be made. If the basicity of the amine, its steric configuration, and the reaction conditions, i. e., higher temperatures and greater excesses of the amine, are favorable, then the tetrasubstituted ethylene can be substantially the sole product of the reaction.

These considerations of the various controlling'fac tors on the aforesaid outlinedequilibria are further illustrated in the following examples in which the pa s given are by weight and in which all reactions and subsequent manipulations are carried out in an inert atmosphere (dry N These examples are submitted only to further illustrate the processes and new products of the present invention and are in no way to be taken as limitative thereof.

EXAMPLE I CHrC r 2 In a glass reactor fitted with a short packed distillation column, condensing means, and a distillation takeoff head, amixture of 15.5 parts of a,a-dimethoxytrimethylamine and 18.5 parts of anhydrous pyrrolidine' was heated by means of an oil bath at 102110 C., and the dimethylamine and methanol formed by such heating were removed through the distillation head as formed. Heating was continued until no further dimethylamine or methanol was formed. The reaction residue Was then purified by further distillation. There was thus obtained 12.0 parts (50% of theory) of crude bis(.N- pyrrolidinyl)methoxymethane as a clear, colorless liquid boiling at 5964 C. under a pressure corresponding to 0.35 mm. of mercury. Upon redisti'llation there was obtained 8.0 parts of pure bis(N-pyrrolidinyl)methoxy methane as a colorless mobile liquid boiling at 7 374 C. under a pressure corresponding to 0.85 mm. ofmercury.

Analysis.-Calcd. for C H N C,65.2%; H, 10.9%; N, 15.2%.

Found: C, 65.2%; H, 10.8%; N, 15.0%.

EXAMPLE II Bis(N-pyrrolidinyl) methoxymethane A mixture of 23.8 parts of a,a-dimethoxytrimethylamine, 28.4 parts of anhydrous pyrrolidine, and 44 parts of benzene was heated at. the reflux with the benzene/ methanol azeotrope, boiling at 58 C. at atmospheric pressure, being removed continuously as it was formed. The dimethylamine formed concurrently was vented to the atmosphere. Heating was continued until the azeotrope no longer distilled over and the benzene was then removed by evaporative distillation. Continued distillation of the residue under reduced pressure afforded 11.1 parts (30% of theory) of bis(N-pyrrolidinyl)methoxymethane as a clear, colorless liquid boiling at 6667 C. under a pressure corresponding to 0.65 mm. of mercury.

7 8 EXAMPLE III (100% of theory) of tetrakis(N-pyrrolidinyDethylene N dimethoxymethylpyrmlidine and tetmkis(N pyr which after recrystallization from ethyl acetate melted rlidinyl)ethylene at 95960 CH -CH1 GHQ-CH2 CHgCHg CH CHZ GI -0H (3H2 (|]H2+(CH3)2NCH(O oHm NCH(OCH l: N:lCHOOH;+ Ii i N]C=C|:-N CHzCH2 OHFCHZ g GIL-CH2 z CHz-CH; 2

EXAMPLE VI A mixture of 23.8 parts of u,ot-dimethoxytrimethyl amine and 28.4 parts of dry pyrrolidine was heated in a N-dimethoxymethylpiperidine, bis(N-piperidz'no)methreactor as in Example I to a maximum temperature of oxyme thane, and tetrakis(N-pfperidino)ethylene CHPCH Ont-0H H O NH+(CEI3)1.NCH(OCH3)ZHZO NCH(OCH-a)z 0H.0H CHz-CH;

125 C. until distillation of dimethylamine and metha- A mixture of 23.8 parts of a,tx-dimethoxytrimethylnol ceased. Distillation of the residue under reduced amine and 37.5 parts of dry piperidine was heated in a pressure aiforded 4.8 parts (17% of theory) of N- reactor as described in Example I in an oil bath at for-mylpyrrolidine dimethyl acetal, i.e., N-dimethoxy- 100l40 C. until distillation of dimethylamine and methylpyrrolidine, as a clear, colorless liquid boiling at methanol ceased. Distillation of the reaction residue 63 C. under a pressure corresponding to mm. of 25 under reduced pressure afiorded 4.0 parts (12.5% of mercury. The product on redistillation at atmospheric theory) of N-formylpiperidine dimethyl acetal, i.e., N- pressure boiled at 160 C. dimethoxymethylpiperidine, as a clear, colorless liquid Analysis.Calcd. for C7H15NO2I C, 57.9%; H, boiling at 76 C. under a pressure corresponding to 22 10.4%; N, 9.6%. Found: C, 58.4%; H, 10.5%; rnm. of mercury. N, 9.6%. Analysis.Calcd. for C H NO N, 8.8%. Found:

Continued distillation of the residue from the isola- N, 8.6%. tion of the N-dimethoxymethylpyrrolidine to a bath tem- Continued distillation of the residue from the isolation perature of 170 C. under a pressure corresponding to of the above N-dimethoxymethylpiperidine at a bath 0.1 mm. of mercury afforded 2.2 parts (8% of theory) temperature of 160 C. afforded 18.7 parts (44% of of bis(N-pyrrolidinyl)methoxyrnethane. Upon redistiltheory) of bis(piperidino)methoxymethane as a clear, lation the product was obtained as a clear, colorless colorless liquid boiling at 105 C. under a pressure corliquid boiling at 69 C. under a pressure corresponding responding to 4 mm. of mercury; 11 1.4798. to 0.80 mm. of mercury. The still residue from the iso- Analysis.Calcd. for C H N O: C, 67.9%; H,

lation of the above bis(N-pyrrolidinyl)methoxymethane 11.4%; N, 13.2%. Found: C, 67.9%; H, 11.4%; crystallized on cooling. On recrystallization from ethyl N, 12.9%.

acetate or acetonitrile, the pure tetrakis(N-pyrrolidinyl) The still residue from the distillation of the above ethylene was obtained as white needles melting at 94- bis(piperidino)methoxymethane solidified on cooling. 95 C., fluorescing under ultraviolet light (3660 A.), There was thus obtained 14.5 parts (40% of theory) of and chemiluminescing on exposure to air. tetrakis(piperidino)ethylene as a crystalline product Analysis.Calcd. for C H N C, 71.0%; H, 10.6%; melting at 53-59 C. After recrystallization from ethyl N, 18.4%. Found: C, 71.2%; H, 10.6%; N, 18.5%. acetate, the purified product melted at 59.0-61.5 C.

EXAMPLE IV Analysis.Calcd. for C H N C, 73.3%; H, 11.2%;

N, 15.5%. Found: C, 72.8%; H, 11.9%; N, 15.5%.

Tetrakis( N -pyrr0lidinyl ethylene EXAMPLE VII A mixture of 119 parts of a,ot-dimethoxytrimethylamine and 142 parts of dry pyrrolidine in a glass reactor T ellakis(N-piperidino)ethylene was attached to a still and heated under reflux in an oil A mixture of 595 parts of mwdimfithoxytrimethyb 854060 Over P penod 33 Parts amine and 170 parts (2.0 molar proportions based on of dimethylamine was collected In a cold trap connected the amine) of anhydrous piperidine in a glass reactor to the still. Methanol was then removed by distillation 55 was attached IO a still as in Example I and was heated from the mixture as the temperature, of the oil bath was at the reflux in an oil bath until evolution of dimethylslowly Tamed Over a three'hour penod to and amine ceased. Methanol was then distilled from the reheld at 2004120 two hours total of 66 parts action mixture as the temperature of the heating bath was of methanol was obtained. On cooling to 90 C. the Slowly raised Over a period of eight hours to C.

reaction residue crystallized. There was thus obtained A total of 31 6 parts (theory, 32 parts) of methanol was 149's parts (.98% of theory) f P obtained. Removal of all material (including excess ethylene which after crystallization from acetomtrile piperidine) volatile below a bath temperature of C.

O melted at 91*93 while maintaining the reactor at a pressure correspond- EXAMPLE V ing to 0.55 mm. of mercury, alforded parts (89% of A glass reactor charged with 10.75 parts of bis(N- i 0f e i (pip idinwethylene as a residue pyrrolidiny-l)rnethoxymethane was fitted to a distillation Whlch crystlllfled 011 l; After Tecfystfllhzahon still and heated in an oil bath at 225 C. The methanol from m l the pr melted at 5961 C. formed was removed by distillation. At the end of 1.5 hours of heating, there had been collected 1.8 parts 7 EXAMPLE VH1 (theory 1.87 parts) of methanol. The reaction residue Bis(N-m0rph0lino)methoxymethane and tetrakz'ssolidified on cooling and there was thus obtained 8.9 parts (N-m0rph0lin0)ethy lene CH2CH2 /CHz-Cg2 /CH2C\2 /OHZCI\I\1 0 \NH+(CH3)2NCH(OCH3)2 [O /N:|CHOCHz |i0 N:|C=Cl:-N /0] CH2 CH2 CH2CH2 z G a-C 2 z CH2CH2 3 .9 10 A mixture of 26.8 parts of a,tx-dimethoxytrimethylafforded 20.4 parts (83% of theory) of l,l',3,3'-tetraamine and 41.2 parts of anhydrous morpholine was methyl-A -bi(imidazolidine) as a clear, colorless liquid heated in a glass reactor attached to a still as in Example which boiled at 9697 C. under a pressure correspond- I at the reflux in an oil bath at 98-110 C. After 2.5 ing to 8 mm. of mercury and which crystallized on coolhours under these conditions, dimethylamine evolution ing to a low melting solid. This bicyclic tetrakis(diceased. Methanol was then distilled from the reaction substitutedamino)ethylene :chemiluminesces strongly in mixture as the temperature of the bath was slowly raised air with evolution of heat. Solutions of the product in over a period of four hours to 200 C. and held at that cyclohexane also chernilurninesce strongly in the prestemperature for an additional 0.5 hour. Continued disence of air.

tillation under reduced pressure afi'orded 20.4 parts (42% Analysis.-Calcd. for C H N C, 61.2%; H, 10.3%.

of theory) of bis(morpholino)methoxymethane as a Found: C, 61.2%; H, 10.5%.

clear, colorless liquid boiling at 103108 C. under a EXAMPLE XI pressure corresponding to '1.01,.2 mm. of mercury. On

cooling, the product crystallized and melted at 64-67.5 r 'tetmethyl'mz 'bl(lmldaz0lldme) C. after recrystallization from -rnethylcyclohexane. 10 AS in Example a 'fi 0f 37 Parts of dad-dime- Anaylysis -Ca1cd, 01- C H N O C, 55.5%; H, thoxytrimethylamine and 85 parts of N,N-diethylethylene 9.3%; N, 13.0%. Found: C, 55.7%; H, 9.2%; diamine was heated under reflux in an oil bath at 85- N, 13.2%. 105 C. until evolution of dirnethylamine became slow. On cooling, the still residue from the isolation of Methanol was then distilled from the reaction mixture as the above bis(morpholino)methoxyrnethane solidified. 20 the bath temperature was slowly raised until a final tem- There Was thus obtained 21.8 parts (41% of theory) of perature of 200 C. was reached. Continued distillation tetrakis(morpholino)ethylene. After recrystallization of the reaction mixture under reduced pressure afforded from ethyl acetate, the product melted at 170-171 C. 69.5 parts (76% of theory) of 1,1,3,3-tetraethyl-A Analysis.-'Calcd. for C H N O N, 15.2%. Found: -bi(imidazolidine) as a light yellow liquid boiling at 79 N, 15.4%. 82 C. under a pressure corresponding to 0.5 mm. of

EXAMPLE IX Bis[N (N '-methyl )pzperazinyl] methoxymethane and tetrakis[N N '-methyl p ip emziny l ethylene As in Example I, a mixture of 11.9 parts of a,m-di mercury. The product chemiluminesced strongly on exmethoxytrimet-hylamine and 20.0 parts of N-methylpiperposure to air. azine was heated at 130210 C. until evolution of di- Anzzlysis.-Calcd. for C H N C, 66.6%; H, 11.2%;

methylamine and methanol had ceased. Continued dis- N, 22.2%. Found: C, 66.9%; H, 11.3%; N, 21.9%. tillation of the reaction mixture under reduced pressure afforded 7.8 parts (32% of theory) of bis[N-(N'- EXAMPLE XII methyl)piperazinyl]methoxymethane as a clear, colorless 1 3' 2,2' liquid boiling at 106-110 C. under a pressure corresponding to 0,9 mn of mercury A mlXtlll'fi Of 23.8 parts Of a,a-d1methoxytr1methyl- Analysis.Calcd. ,for C I-1 N 01 C, 59.5%; H, amine and 20.4 parts of N-ethyl-N-methylethylenedi- 108%, Fou d; C, 599%; I-I, 1.0 8% amine was heated in a reactor as described in ExampleI On cooling, the still residue from the isolation of the a bait} tempefijltllfe 0f C- r a pe o Of 81X above substituted methoxymethane crystallized. There hours, W t edlmcthy amlne and methanol evolved in wa thu btained 11,1 parts (53% of theory) of t t the reaction being removed by distillation. Essent1ally kis[N-(N'-meth l) i erazi n thyle which fter 55 the theoretical quantity of the latter was obtained. Concrystallization from acetonitrile melted at 79.0-80.5 C. tinued distillation of the reaction residue under reduced Analysis.-Calcd. for C H 'N N, 26.6%. Found: pressure afforded 17.2 parts (77% of theory) of 1,3- N, 26.6%. diethyl-1,3-dimethy1-A '-bi(imidazolidine) as a light As in Example I, a mixture .of 29.8 parts of oc,ocdi yellow liquid boiling at 8082 C. under a pressure cormethoxytrimethylamine and 23.3 parts of N,N'-dimethylresponding to 0.25 mm. of mercury. The product chemethylenediamine was heated in an oil bath at '100-156 iluminesced strongly on exposure to air. C. until evolution of dirnethylamine and methanol had Analysis.Calcd. for C H N C, 64.2%; H, 10.8%;

ceased. Continued distillation of the reaction residue N, 25.0%. Found: C, 64.2%; H, 11.0%; 'N, 24.4%.

EXAMPLE XIII 1 ,3 -dimethyl-2-methoxyhexahydropyridine and '1 ,1 3,3 -te tramethyl-A -bi (hexahydropyrimidine) r r E /oH2N CH3 GHQ-N NCH CH3NH(CH2)3NHOH3 (CH3)2NCH(OCH3)2 H2C\ /o\ HzC\ /0=o\ /CHz CHTJTI H CH2N N-CHz CH3 CH CH3 Example II was substantially duplicated using 73.4 parts EXAMPLE XV of a,a-dimethoxytrimethylamine, 62.6 parts of N,N- dimethyl-1,3-propanediamine, and 132 parts of benzene. Distillation of the reaction residue afforded 20.8 parts (24% of theory) of 1,3-dimethyl-2-methoxyhexahydropyrimidine as a colorless liquid boiling at 6266 C. under a pressure corresponding to 25 mm. of mercury.

Analysis.Calcd. for C H N O: C, 58.3%; H, 11.2%; N, 19.4%. Found: C, 58.6%; H, 11.2%; N, 19.4%.

5 Di-n-propylaminodimethoxymethane and bis(di-n-pr0- pylamino)methoxymethane Example XIV was substantially duplicated using 23.8 parts of a,u-dimethoxytrimethylamine and 44.5 parts of Continued distillation of the reaction residue after re- -p py With bath 'ffimpeffitures ranging from moval of the 1,3-dimethyl-2-methoxyhexahydropyrimi- 100 C. to 160 C. over an 8-hour reaction period with dine afforded 23,3 parts (34% f theory) f 1,133. removal of the methanol and dimethylamine as formed. Ietramethyl-A '-bi(hexahydropyrimidine) as a light yel- Continued distillation of the residue at reduced pressure low liquid boiling at 104105 C. under a pressure corafforded P of y) of -P PY responding to 8,5 mm, of mercury, The product lumi. formamide dimethyl acetal, 1.6., di-n-propylaminodimethnesced strongly on exposure to air. oxymethane, as a clear, colorless liquid boiling at 6870 Analysis.-Calcd. for C H N N, 25.0%. Found: C. under a pressure corresponding to 13 mm. of mercury. N, 25.1%. Analysis.Calcd. for C H NO N, 8.0%. Found:

Continued distillation of the reaction mixture upon removal of the above amide acetal atforded 3.4 parts (7% of theory) of bis(di-n-propylamino)methoxymethane as a clear, colorless liquid boiling at 105 C. under a pressure corresponding to 7 mm. of mercury.

EXAMPLE XIV 1-dimeth0xymethyl-2,5-dimethylpyrrolidine and Bis[N- (2,5-dimethylpyrrolidinyl) ]meth0xymethane A mixture of 11.9 parts of a,a-dimethoxytrimethy1- amine and 19.8 parts of 2,5-dimethylpyrrolidine was heated in a reactor as described in Example I with the Analysis.Calcd. for C H N O: C, 68.8%; H, bath temperature slowly rising over a period of 4.5 hours 13.2%; N, 11.5%. Found: C, 68.8%; H, 12.9%; N, from 113-175 C. and the methanol and dimethylamine 11.6%.

EXAMPLE XVI Bis[bis(dimethlyamin0) methyleneamino] methoxymethane and tetrakis[bis(dimethylwmino)methyleneamin0]ethylene formed during the heating being removed by distillation. The bath temperature was then raised to 200 C. and held for two hours, distilling off all material boiling below 110 C. from the reaction mixture. Continued disin Example I over a period of 2-3 hours with the bath tillation under reduced pressure afforded 7.0 parts (40% temperature at about femoving the dimethyl of theory) of N-formyl-2,5-dimethylpyrrolidine dimethyl amine and methanol formed during the reaction- The acetal, Le 1-dimethoXYmethypzydimethylpyrrolidine, residual liquid was distilled under reduced pressure to as a clear, colorless liquid boiling at 90-91 C. under a affofd 105 Parts 9 of theory) of blswlswlmethyl' pressure Corresponding to 49 mm of mercury. amino)rnethyleneamlno]methoxymethane as a clear, col- Aalysl-S' Ca1cd' for CQHISNOZ: C, 614%; H 11.0% orless lrquld boiling at 9698 C. under a pressure cor- N, 8 1% Found: C, 626%; H, 11'1%; N, 8.7% respondmg to 0.9 mm. of mercury; 11 1.4863.

Continued distillation of the reaction mixture after Analysls' calcd'for C1H28N60: 52'9%;H104%;

removal of the 1-dimethoxymethyl-2,5-dimethylpyrro Found: 523%; 102%;

A portion (8 parts) of the above bis[bis(dimethyll1d1ne afforded 3.54 parts (15% of theory) of b1s[N-( amino)methyleneamino]methoxymethane was heated at dimethylpyrrolidillyl)1methoxymethane as a clear, color 250 C. until no further methanol was evolved. The re- 1658 liquid boiling at under a Pressure action residue was cooled and the resultant crystalline responding to 24 of ysolid recrystallized three times from ethyl acetate to af- Analysis.Calcd. for C H N 01 70.0%; ford 3.1 parts (43% of theory) of the tetrakis[bis(di- 11.7%; N, 11.6%. Found: C, 70.3%; H, 11.6%; N, methylamino)methyleneaminoJethylene as white crys- 12.4%. tals melting at 7072 C.

A mixture of 11.9 parts of a,a-dimet-hoxytrimethy1- amine and 23 parts (two molar proportions based on the methane) of 1,1,3,3-tetrarnethylguanidine was heated as C, 52.5%; H, Found: C, 52.2%; H, 9.8%; N,

EXAMPLE XVII 1,133,3 rezmbmz l-A -bitimidazolidine) A mixture of 22.2 parts of a, x-dimethoxytrimethylamine, 45 parts of N,N'-dibenzylethylenediamine, and 66 parts of benzene was heated under refiux in an oil bath at 83103 C. until the evolution of dimethylamine became slow. Methanol was then removed by distillation as the methanol/benzene azeotrope. There was obtained 45 ml. of distillate, B.P. 52-58" C. (theory 37.5 m1, B.P. 58 C.). All volatiles were than removed from the reaction mixture at room temperature and under a pressure corresponding to 0.1 mm. of mercury. The solid residue of crude product Weighed 47.9 g. (theory 46.8 g.). After two crystallizations from ethyl acetate the very light yellow needles of 1,1,3,3 '-tetrabenzyl-A '-bi(imidazolidine) melted at 162-164 C.

Analysis.Calcd. for C H N N, 11.2%. N, 10.8%.

This invention is generic to a new process for the preparation of new tetrakis(disubstitutedamino)ethylenes, a generically new class of bis(disubstitutedamino)monohydrocarbyloxyhydrocarbons, a process for the preparation thereof, and also to new types of tetrakis(disubstitutedamino)ethylenes, especially those wherein the amine nitrogens form part of a heterocyclic structure The reaction involves a condensation between the req- Found:

quisite secondary amine and the desired amide acetal or ketal whereby the amine hydrogen in the coreactant secondary amines unites with one hydrocarbyloxy group of the amide acetal or ketal to liberate one molar proportion of the resultant hydroxy-substituted hydrocarbon, e.g., alcohol or phenol, and/or the amine moiety, i.e., the amine nitrogen and two hydrocarbon radical substituents thereon, replace the amine moiety in the starting amine acetal, liberating the said amine moiety in the form of the amine resulting from addition of the entering secondary amine hydrogen to the replaced moiety. In the case of the formamide acetals, provided sufficient quantities of the secondary amine coreactant are present and the reaction conditions are sufficiently stringent, the reaction can go beyond the stage of the formation of the new amide acetal involving the entering amine moiety and the bis disubstitutedamino monohydrocarbyloxy hydrocarbon and form the tetrakis(disubstitutedamino)ethylenes, all as in accord with the stoichiometry discussed in detail in the foregoing.

The requisite amide acetal and ketal intermediates can be prepared by the method of Meerwein, Angew, Chem. 71, 530 (1959), by reaction between a hydrocarbon ether, a hydrocarbyl fluoride, and-silver fluoborate to form a trihydroc'arbyloxonium fluoborate which is then reacted with the requisite N,N-dihydrocarbyl-substituted carbo'xamide to form the intermediate oxonium fluoborate derivative of the amide, i.e., an a-(N,N-dihydrocarbylamino) a '(hydrocarbyloxy)hydrocarbonium 'fluob'orate, which is subsequently further reacted with an alkali metal alcoholate to form the desired amide acetal or ketal and, as a co-product, the alkali metal fiuoborate. Also, as disclosed in the same reference, the intermediate higher amide acetals and ketals can be prepared by alcohol exchange with the lower amide acetals and ketals in accord with the following stoichiometry:

R NCR'(OR") +2R"'OH R NCR'(OR"') +2ROH where R is of greater carbon content than R".

In view of the inate complexity of the silver fluoborate synthesis, the latter, i;e., the alcohol exchange route, will, for convenience reasons, generally be preferred. Thus, the silver fluoborate synthesis will normally be used to prepare the first member of the series, i.e., the dimethyl acetal of N,N-dimethylformamide, which will then be used in alcohol exchange to prepare any desired higher hydrocarbyloxy amide acetals. The same generally applies to any desired higher hydrocarbylamino amide acetals and ketals in which an amine exchange reaction in accord with the following stoichiometry will serve to prepare any desired higher hydrocarbylamino amide acetals and ketals:

where R is ofgreater carbon content than R.

In both these alcohol and amine exchange reactions, the cyclic products can also be obtained, i.e., by the use of a glycol to obtain the cyclic hydrocarbyloxy moiety or by use of a cyclic secondary amine to obtain the cyclic amino moiety of the amide acetals and ketals.

The preferred method of preparing the necessary intermediate amide acetals and ketals involves the reaction of an alkali metal or alakaline earth metal salt of the desired alcohol or phenol with the requisite a,a-dihalosubstituted tertiary amine in accord with the following wherein R and R", which can be alike or different, are monovalent alkyl or cycloalkyl radicals of no more than 8 carbons each, which can be together joined as a divalent radical with the intervening nitrogen to form a saturated heterocycle of 3-7 ring members (the broken lines indicating the possibility of joinder between the groups terminating the same), said divalent radicals containing no more than 26 carbons each; R is hydrogen or a rhonovalent alkyl, aryl, aralkyl, alkaryl, or cycloalkyl hydrocarbon radical of no more than 8 carbons or R. l N RI! the Xs, which can be alike or different, are halogens of atomic No. from 9-35; M is an alkali metal or an alkaline earth metal; R is a monovalent alkyl, aryl, aralkyl, alkaryl, or cycloalkyl radical of no more than 8 carbons; and m and n are integers from 1-2, inclusive, depending on the valence of the metal M and such that m]-n=3.

When n is 2, the R radicals can be together joined to form with the intervening carbon and two oxygens a 1,3-dioxacarbocycle of 5 to 7 ring members. This preferred synthesis of the intermediates forms the subject of the coassigned copending application of Brown U.S. Patent No. 3,092,637.

In addition to the aforesaid defined new bis(disubstitutedamino)-a-hydrocarbyloxyhydrocarbons and the new, particularly cyclic, tetrakis(disubstitutedamino) ethylenes'and the necessary amide acetal or ketal and secondary amine coreactants given in'the foregoing detailed examples, other such coreactants of these same generic types can be so similarly used to give still further species Within the purview of the present broad product invention. Thus, there can be used such other formamide acetals as N-(dimethoxymethyl)-N-methyl-n-octylamine, N-diethoxymethyldiisobutylamine, N-diethoxymethyl-N- ethyl-p-toluidine, N-diethoxymethylpyrrolidine, N diisopropoxymethylmorpholine, N,N-dim"ethylformamide dimethyl acetal and the like. In preparing the new tetrakis (disubstitutedamino)ethylenes and in particular the especially outstanding cyclic tetrakis(disubstitutedamino) ethylenes, there can be used such other secondary amines as ethyleneimine, i.e., aziridine, azetidine, i.e., azacyclobutane, perhydroazepine, A -pyrroline, i.e., 2,5-dihydroazoline, 1,2,2-trimethylhydrazine, N,N-di-n-dodecyclethleneldiamine and the like. Reaction of these additional amine species with the dimethyl acetal of N,N-dimethylformamide results, respectively, in the formation of the following tetrakis(cyclic and acyclic disubstitutedamino) ethylenes of the present invention: 1,1,2,2-tetrakis(1- aziridinyl ethylene, 1, l,2,2,-tetrakis( l-azetidinyl ethylene, 1,1,2,2 tetrakis(1 hexahydroazepinyl)ethylene, 1,1,2,2- tetrakis l-2,5-dihydroazolinyl ethylene, i.e., 1,1,2,2-tetrakis(1-A -pyrrolinyl)ethylene, 1,1,2,2 tetrakis[1 (1,2,2- trimethylhydrazinyl) ]ethylene, l,l,3,3'-tetra-n dodecyl- A '-bi(imidazolidine) and the like.

Further, the invention is generic to the use of such amide ketals as N,N-dimethylbenzamide dimethyl acetal, i.e., a,ot-dimethoxyphenyldimethylamine, N-acetylpyrrolidine diethyl ketal, i.e., l-(a, x-diethoxyethyl)pyrrolidine, N,N-dimethylcaproic acid amide dimethyl ketal, i.e., 06,!!- dimethoxy-n-hexyldimethylarnine, N,N-dimethyltrifluoroacetamide dimethyl ketal, i.e., a,oa-dimethoxy-,8,,B,,8-trifluoroethyldimethylamine, and the like, which, using the reaction conditions and variables outlined in the foregoing, on reaction with such cyclic amines or disubstituted diamines as N,N'-dimethylethylenediamine, pyrrolidine, morpholine, N,N-dimethyl-l,3-propanediamine, and the like, will form, respectively, the following bis(disubstitutedamino)monohydrocarbyloxyhydrocarbons of the present invention:

l,3-dimethyl-2-methoxy-Z-phenylimidazoline,

e,a-bis(N-pyrrolidinyl)ethyl ethyl ether,

a,o-bis(morpholino)-n-hexyl methyl ether,

1,3 -dimethyl-Z-trifluoromethyl-Z-rnethoxyhexahydropyrimidine, and the like.

The new 'bis(disubstitutedamino)monohydrocarbyloxyhydrocarbons of the present invention are strong bases and accordingly are useful for catalysis of base-catalyzed reactions, especially in organic systems due to their solubility therein, and particularly in catalyzing such reactions as: the addition of alcohols to a-B unsaturated nitriles, cyanoethylation reactions in general using acrylonitrile, additions to activated double bonds such as illustrated in US. 2,822,376, and the like. They are also useful as water scavengers in organic systems, particularly in view of their good organic solubility, and especially because unlike other organic-soluble water scavengers they result in non-corrosive products.

These new products find use as chemical intermediates in condensing with active methylene compounds, forming dihydrocarbylaminoethylene derivatives. More particularly, these new products can be condensed with active methylene compounds, such as malononitrile and the like, to form the dihydrocarbylaminomethylene malononitrile as illustrated with different intermediates but with the same product by Eiden, Angew. Chem. 72, 77 (1960), and by Hafner et al., ibid., 71, 672 (1959).

These new bis(disubstitutedamino)monohydrocarbyloxyhydrocarbons are also useful in the formation of the corresponding tetrakis(disubstitutedamino)ethylenes by direct heating. The tetrakis(disubstitutedamino)ethylenes are generically useful as high energy fuels for rocket and space propulsion. These tetrakis(disubstitutedamino) ethylene-s have specific impulses in the ranges of those of hydrazine and methylhydrazine with N HNO or other like strong oxidizing agents under rocket motor conditions.

The tetrakis(disubstitutedamino)ethylenes are especially useful as high energy fuels since they exhibit not only high specific impulses but also high heats of combustion. Thus, the heat of combustion of l,3'-diet-hyl-1',3-dimethyl- A -bi(imidazolidine) is 8770 cal./g. and that of 1,1, 3,3'-tetraethyl-A '-bi(imidazolidine) is 8970-9010 cal./g. The l,1,3,3'-tetramethyl-A '-bi(imidazolidine) is so active that is spontaneously fires when pressured to about 40 p.s.i. with oxygen. Accordingly, a specific value for the heat of combustion thereof has not been obtained, but it is obviously high.

These new tetrakis(disubstitutedamino)ethylenes are also generically useful as moderate to strong organic redu-cing agents. Thus, they can successfully carry out such reductions as S O 280 MnO MnO and the like.

These new tetrakis(disubstitutedamino)ethylenes are also generically useful as oxygen scavengers and serve thereby, for instance, as gasoline stabilizers, especially for the more conventional leaded gas-olines, to prevent deterioration of the fuels on standing. The tetrakis(disubstitutedamino)ethylenes are not only useful as oxygen scavengers but form basis for a suitable analytical procedure for determining the amount of oxygen in a system by simply putting a known quantity of the aminoethylene in the system in question and determining the amount of carbonyl formed when reaction was complete.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The process which comprises reacting together, at a temperature in the range 25-250 C.,

(A) an amide acetal of the formula wherein:

(1) the two -Rs, which need not be the same, are

selected from the group consisting of monovalent alkyl and cycloalkyl of no more than 8 carbons each and divalent alkylene of 1-6 carbons; and

(2) the two R"s, which need not be the same,

are selected from the group consisting of monovalent alkyl, aryl, aralkyl, alkaryl and cycloalkyl of no more than 8 carbons each and divalent alkylene of 2-4 carbons, and

(B) a secondary amine of the formula R" NH wherein: the two R"s, which need not be the same, are selected from the group consisting of:

(l) monovalent alkyl, cycloalkyl, oxahydrocarbon, azahydrocarbon, and oxaazahydrocarbon of no more than 8 carbons, each nitrogen carrying no more than one methyl; and

(2) divalent alkylene, oxahydrocarbon, and azahydrocarbon of 1-6 carbons.

2. The process of claim 1 where in the amide acetal is an a,a-dialkoxytrialkylamine.

3. The process of claim 1 wherein the amide acetal is a,ot-dimethoxytrimethylamine.

4. The process of claim 2 wherein the amine is pyrrolidine.

5. The process of claim 2 wherein the amine is piperidine.

'6. The process of claim 2 wherein the amine is morpholine.

7. The process of claim 2 wherein the amine is N- methylpiperazine.

8. The process of claim 2 wherein the amine is N,N- dimethylethylenediamine.

9. The process of claim 2 wherein the amine is N,N- diethylethylenediamine.

10. The process of claim 2 wherein the amine is N- ethyl-N-m-ethylethylenediamine.

11. The process of claim 2 wherein the amine is N- N'-dimethyl-1,3-propanediamine.

12. The process of claim 2 wherein the amine is 2,5- dimethylpyrrolidine.

13. The process of claim 2 wherein the amine is din-propylamine.

17 18 14. The process of claim 2 wherein the amine is 1,1, 18. Tetrakis(N-pyrrolidinyl)ethylene. 3,3-tetrarnethylguanidine. 19. Bis(N-piperidino)methoxymethane.

15. The process of claim 2 wherein the amine is N,N- 20. Tetrakis(N-piperidino)ethy1ene. dibenzylethylenediamine. 21. Bis(N-morpholino)rnethoxyrnethane.

16. A compound of the group consisting of: 5 22. Tetrakis(N-rnorpho1ino)ethy1ene.

23. Bis[N-(N-methy1)piperazinyl]methoxymethane.

24. Tetrakis[N-(N'-methy1)piperazinylJethylene. 25. 1,1',3,3'-tetramethy1-A '-bi(imidazolidine).

CHORQ, Q (311032, 6:? 26. 1,1',3,3-tetraethy1-A i;-lii(gn;idazolidige).1d

27. '1,3'-diethy1-1,3-dimet y -A -bi-I(irni azoi ine 7 10 28. 1,3-dimethy1-2-methoxyhexahydropyrimidine.

29. 1,1,3,3' tetramethyl A bi(hexahydropyrirniand dine).

R4 R4 30. Dimethoxymethyl-Z,S-dimethylpyrrolidine.

I l 31. BiS[N (2,5-dimethylpyrro1idinyi)]rneth0xymeth- 7 f? Q Q 32. Tetrakis[bis(dirnethy1amino)methy1enearnino1eth- L 1 1; ylene.

I 33. 1,1',3,3'-tetrabenzy1-A '-bi(imidazolidine).

34. Bis(di-n-propy1amine)methoxyrnethane. wherelm 35. Bis[bis(dimethylarnino)methyleneamino]methoxy- (A) R is selected from the group consisting of alkyl, h

.aryl, aralkyl, alkaryl and cycloalkyl of up to 8 carbons; References Cited by the Examiner (B) R and R are selected from the group consisting UNITED STATES PATENTS of rnonovalent alkyl, cycloalkyl, oxahydrocarbon azahydrocarbon, and oxaazahydrocarbon of up to 8 2437963 3/1948 Langmulr et a1 252*305 carbons, each depicted nitrogen carrying 110 more 2,440,915 5/1948 Roehr 252305 than one methyl, and divalent alkylene of 2-6 car- 2,620,311 12/1952 Bleeker 252 301-2 bans; 2,681,317 6/1'954 Gr-ossrnan 252'30 1.2 (C) -R and R are selected from the group consisting 2,916,490 12/1959 schenck et a1 260-247 of monovalent alkyl, cycloalkyl, oxahydrocarbon, 2,993,894 7/1961 Marcus et a1 260 247 azahydrocarbon, and oxaazahydrocarbon of up to 8 WALTER A. MODANCE, Primary Examiner.

carbons, each depicted nitrogen carrying no more than one methyl, :and divalent alkylene of -2-6 car- REUBEN EPSTEIN CARL QUARFORTH bons; and Examiners. (D) Q is alkylene of 1-4 carbons. W. T. HOUGH, L. A. SEBASTIAN, ROBERT T. BOND, 17. Bis(N-pyrrolidinyl)methoxymethane. Assistant Examiners. 

1. THE PROCESS WHICH COMPRISES REACTING TOGETHER, AT A TEMPERATURE IN THE RANGE 25-250*C. (A) AN AMIDE ACETL OF THE FORMULA
 16. A COMPOUND OF THE GROUP CONSISTING OF:
 21. BIS(N-MORPHOLINO) METHOXYMETHANE. 